Novel macromonomer compositions

ABSTRACT

Novel compositions of homopolymers and copolymers containing an olefinic polymerizable end group wherein the monomeric units comprise methacrylate, acrylate, acrylic acid, styrene, vinyl esters, acrylonitrile, methacrylonitrile, vinyl halides, vinylidene halides, substituted butadienes, ethylene-sulfonic acid derivatives, acrylamide derivatives, methacrylamide derivatives, and other monomers, and mixtures thereof are disclosed.

This application is a continuation of U.S. patent application Ser. No.113,928, filed Oct. 26, 1987 now abandoned, which was acontinuation-in-part of U.S. patent application Ser. No. 910,589, filedSept. 23, 1986, now abandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to novel compositions of homopolymers andcopolymers containing an olefinic polymerizable end group wherein themonomeric units comprise methacrylate, acrylate, styrene, vinyl esters,acrylonitrile, methacrylonitrile, vinyl halides, vinylidene halides,substituted butadienes, ethylenesulfonic acid derivatives, acrylamidederivatives, methacrylamide derivatives, and other monomers, andmixtures thereof.

2. Background

Macromonomers, that is, polymers containing an olefinic polymerizableend group, are known in the art. For example, Smirnov et al., Dokl.Akad. Nauk USSR, 255, 609-612 (1980) discuss the production of polymershaving a terminal olefinic group using cobalt complexes of porphyrins asa catalytic chain transfer agent. Cacioli et al. J. Macromol., A23,839-852 (1986) describe the preparation, using Co(II)tetraphenylporphyrin as catalyst, of methyl methacrylate oligomers ofvarious number-average molecular weights having terminal double bondsand describe the usefulness of such macromonomers in the production ofgraft polymers. Abbey et al., Proceedings of the ACS Division ofPolymeric Materials Science and Engineering, 55, 235-238 (1986) discussterminal olefinic polymers produced using a cobaloxime chain transferagent. The authors state that the dimer can be isolated at 99% purity.

Using present art processes, however, the percentage of macromonomersobtained is often very low, and is always less than about 80 mol %.Moreover, using current methods, isolation of macromonomers of greaterthan about 2 or 3 monomer units from terminally saturatednon-polymerizable polymers which are also generated by such processes isnot possible.

Novel compositions containing a higher percentage of macromonomer areneeded in order to permit more effective utilization of these compoundsin the production of graft polymers and other polymeric moieties.

SUMMARY OF THE INVENTION

The present invention provides a novel macromonomer compositioncomprising at least about B0 mol % of a macromonomer having:

(I) an end group of the formula

    C(X.sub.1)(X.sub.2)═C(X.sub.3)(CH.sub.2).sub.n ; and

(II) at least 50 and up to about 10,000 monomeric units linked to theend group, said units being independently selected from a compound ofthe formula

    --CR.sub.1 (CR.sub.2 ═CR.sub.3).sub.m C(R.sub.4)(R.sub.5));

wherein:

n is 0 or 1;

X₁ and X₂ independently are H or a polar or nonpolar substitutent thatis inert under polymerizing conditions, provided that when n is 0, atleast one is not H and provided that when n is 1, both are H;

X₃ is H or a polar or nonpolar substituent that is inert underpolymerizing cond itions, provided that when n is O, X₃ is H;

m is 0 or 1;

R₁, R₂ and R₃, independently, are H or a polar or nonpolar substituentthat is inert under polymerizing conditions;

R₄ and R₅, independently, are H or a polar or nonpolar substituent thatis inert under polymerizing conditions, provided that where m is 0, atleast one is not H;

provided that:

each monomeric unit has polymerizing compatability with any adjacentmonomeric unit.

The present invention also provides a novel macromonomer compositioncomprising at least about 80 mol % of a macromonomer having:

(I) an end group of the formula

    C(X.sub.1)(X.sub.2)═C(X.sub.3)(CH.sub.2).sub.n ;

and

(II) at least 3 and up to about 10,000 monomeric units linked to the endgroup, said units being independently seIected from a compound of the

    --CHR.sub.1 (CR.sub.2 ═CR.sub.3).sub.m C(R.sub.4)(R.sub.5));

wherein:

n is 0 or 1;

X₁ and X₂ independent)y are H or a polar or nonpolar substitutent thatis inert under polymerizing conditions, provided that when n is 0, atleast one is not H and provided that when n is 1, both are H;

X₃ is H or a polar or nonpolar substituent that is inert underpolymerizing conditions, provided that when n is O, X₃ is H;

m is 0 or 1;

R₁, R₂ and R₃, independently, are H or a polar or nonpolar substituentthat is inert under polymerizing conditions;

R₄ and R₅, independently, are H or a polar or nonpolar substituent thatis inert under polymerizing conditions, provided that where m is 0, atleast one is not H;

provided that:

(a) each monomeric unit has polymerizing compatability with any adjacentmonomeric unit;

(b) the macromonomer has at least 50 monomeric units linked to the endgroup

when

each n is 1,

each X₁ and X₂ are H,

each X₃ is CO₂ J wherein J is H, C₁ -C₁₂ alkyl, C₂ -C₁₂ alkenyl,glycidyl, C₂ -C₁₂ hydroxyalkyl, allyloxyethyl, 2,4-hexadienyl, C_(x)H_(2x+1-y) F_(y) where x is 1 to 16 and y is 0 to 2x+1, R₆ R₇ N(CH₂)_(z)where R₆ and R₇ are independently C₁ to C₁₂ alkyl and z is 1 to 10, orR₈ R₉ R₁₀ Si(CH₂)_(z) where R₈, R₉ and R₁₀ are independently C₁ to C₁₂alkyl or C₁ to C₁₂ alkoxy and z is 1 to 10,

each m is 0,

each R₁ is H, and

each R₄ and R₅ are CH₃ and CO₂ J wherein J is H, C₁ -C₁₂ alkyl, C₂ -C₁₂alkenyl, glycidyl, C₂ -C₁₂ hydroxyalkyl, allyloxyethyl, 2,4-hexadienyl,C_(x) H_(2x+1-y) F_(y) where x is 1 to 16 and y is 0 to 2x+1, R₆ R₇N(CH₂)_(z) where R₆ and r₇ are independently C₁ to C₁₂ alkyl and z is 1to 10, or R₈ R₉ R₁₀ Si(CH₂)_(z) where R₈, R₉ and R₁₀ are independentlyC₁ to C₁₂ alkyl or C₁ to C₁₂ alkoxy and z is 1 to 10, provided that whenR₄ is CO₂ J R₅ is CH₃ and when R₅ is CO₂ J R₄ is CH₃ ,

that is, the macromonomer is a homomacromonomer of methacrylate; and

(c) the macromonomer has at least 50 monomeric units linked to the endgroup

when

substantially all of the monomeric units in the macromonomer areselected from at least two of the following monomeric units

(i) where

m is 0,

R₁ is H,

R₄ and R₅ are CH₃ and CO₂ J wherein J is H, C₁ -C₁₂ alkyl, C₂ -C₁₂alkenyl, glycidyl, C₂ -C₁₂ hydroxyalkyl, allyloxyethyl, 2,4-hexadienyl,C_(x) H_(2x+1-y) F_(y) where x is 1 to 16 and y is 0 to 2x+1, R₆ R₇N(CH₂)_(z) where R₆ and R₇ are independently C₁ to C₁₂ alkyl and Z is 1to 10, or R₈ R₉ R₁₀ Si(CH₂)_(z) where R₈, R₉ and R₁₀ are independentlyC₁ to C₁₂ alkyl or C₁ to C₁₂ alkoxy and z is 1 to 10, provided that whenR₄ is CO₂ J R₅ is CH₃ and when R₅ is Co₂ J R₄ is CH₃,

that is, methacrylate monomeric units;

(ii) where

m is 0,

R₁ is H,

R₄ and R₅ are CH₃ and CN, provided that when R₄ is CH₃ R₅ is Cn and whenR₅ is CH₃ R₄ is CN, that is, methacrylonitrile monomeric units; and

(iii) where

m is 0,

R₁ is H,

R₄ and R₅ are H and C₆ H₅, provided that when R₄ is H, R₅ is C₆ H₅ andwhen R₅ is H R₄ is C₆ H₅,

that is, styrene monomeric units.

Preferred for reasons of commercial applicability and/or ease ofsynthesis are macromonomer compositions of the above formulas whereinthe macromonomer is a homomacromonomer of methacrylates, that is,

each n is 1,

each X₁ and X₂ are H,

each X₃ is CO₂ J wherein J is H, C₁ -C₁₂ alkyl, C₂ -C₁₂ alkenyl,glycidyl, C₂ -C₁₂ hydroxyalkyl, allyloxyethyl, 2,4-hexadienyl, C_(x)H_(2x+1-y) F_(y) where x is 1 to 16 and y is 0 to 2x+1, R₆ R₇ N(CH₂)_(z) where R₆ and R₇ are independently C₁ to C₁₂ alkyl and z is 1to 10, or R₈ R₉ R₁₀ Si(CH₂)_(z) where R₈, R₉ and R₁₀ are independentlyC₁ to C₁₂ alkyl or C₁ to C₁₂ alkoxy and z is 1 to 10,

each m is 0,

each R₁ is H, and

each R₄ and R₅ are CH₃ and CO₂ J wherein J is H, C₁ -C₁₂ alkyl, C₂ -C₁₂akenyl, glycidyl, C₂ -C₁₂ hydroxyalkyl, allyloxyethyl, 2,4-hexadienyl,C_(x) H_(2x+1-y) F_(y) where x is 1 to 16 and y is 0 to 2x+1, R₆ R₇N(CH₂)_(z) where R₆ and R₇ are independnetly C₁ to C₁₂ alkyl and z is 1to 10, or R₈ R₉ R₁₀ Si(CH₂)_(z) where R₈, R₉ and R₁₀ are independentlyC₁ to C₁₂ alkyl or C₁ to C₁₂ alkoxy and z is 1 to 10, provided that whenR₄ is CO₂ J R₅ is CH₃ and when R₅ is CO₂ J R₄ is CH₃.

DETAILED DESCRIPTION OF THE INVENTION

This invention resides in novel compositions of homopolymers andcopolymers containing an olefinic polymerizable end group. The term"macromonomer" is used herein to describe such terminal olefinicmoieties. More specifically, the term "homomacromonomers" is used todescribe homopolymers having a terminal double bond, and similarily, theterm "comacromonomers" is used to describes copolymers with that endgroup.

The macromonomers of the present invention consist of an end group ofthe formula C(X₁)(X₂)═(X₃)(CH₂)_(n) and up to about 10,000 monomericunits linked to the end group, the units being independently selectedfrom a compound of the formula --CHR₁ (CR₂ ═CR₃)_(m) C(R₄)(R₅)). In afirst embodiment, the invention contemplates that the macromomomer haveat least 50 monomeric units. Thus the number of monomeric units in themacromonomers of the first embodiment could be 50, 51, 52, 53, 54, 55,56, 57, etc., up to about 10,000, and any ranges or combinationstherebetween. In a second embodiment, the invention contemplates thatthe macromonomer have at least 3 monomeric units. Thus the number ofmonomeric units in the macromonomers of the second embodiment could be3, 4, 5, 6, 7, 8, 9, 10, etc., up to about 10,000, and any ranges orcombinations therebetween. Preferred in the first embodiment for reasonsof commercial applicability and/or ease of synthesis are macromonomershaving at least 50 and up to about 1,000 monomeric units. Preferred inthe second embodiment for reasons of commercial applicability and/orease of synthesis are macromonomers having at least 10 and up to about1,000 monomeric units. Most preferred in either embodiment aremacromonomers having at least 100 and up to about 500 monomeric units.

As noted above, groups X₁, X₂, X₃, R₁, R₂, R₃, R₄ and R₅ are defined,with certain qualifications, as being H or a polar or nonpolarsubstituent that is inert under polymerizing conditions. By "polar ornonpolar substituent that is inert under polymerizing conditions", it ismeant a substituent such as, but not limited to, phenyl, carboxylate,acetate, cyano, chloride, fluoride, sulfonate, organic amide, ketoderivative, itaconic derivative, and itaconic anhydride. Polar andnonpolar substituents which would not be inert under polymerizingconditions and thus could not be substituents include acid chlorides inthe presence of water and a mixture of groups of acids or amines.

The mono units thus may comprise, but are not limited to, methacrylatesof the formula CH₃ ═C(CH₃)CO₂ J wherein J is H, C₁ -C₁₂ alkyl, C₂ -C₁₂alkenyl, glycidyl, C₂ -C₁₂ hydroxyalkyl, allyloxyethyl, 2,4-hexadienyl,C_(x) H_(2x+1-y) F_(y) where x is 1 to 16 and y is 0 to 2x +1, R₆ R₇(CH₂)_(z) where R₆ and R₇ are independently C₁ to C₁₂ alkyl and z is 1and z is 1 to 10, or R₈ R₉ R₁₀ Si(CH₂)_(z) where r₈, R₉ and R₁₀ areindependently C₁ to C₁₂ alkyl or C₁ to C₁₂ alkoxy and z is 1 to 10,acrylates of the formula CH₂ ═CHCO₂ J wherein J is H, C₁ -C₁₂ alkyl, C₂-C₁₂ alkenyl, glycidyl, C₂ -C₁₂ hydroxyalkyl, allyloxyethyl,2,4-hexadienyl, C_(x) H_(2x+1-y) F_(y) where x is 1 to 16 and y is 0 to2 x+1, R₆ R₇ N(CH₂)_(z) where R₆ and R₇ are independently C₁ to C₁₂alkyl and z is 1 to 10, or R₈ R₉ R₁₀ Si(CH₂)_(z) where R₈, R₉ and R₁₀are independently C₁ to C₁₂ alkyl or C₁ to C₁₂ alkoxy and z is 1 to 10,styrenes substituted or unsubstituted on the phenyl ring, acrylonitrile,methacrylonitrile, maleic anhydride, fumarate derivatives such asfumaronitrile, dialkylfumarate and fumaric acid, vinyl halides of theformula CH₂ ═CHX wherein X is Cl or F, vinylidene halides of the formulaCH₂ ═C(X)₂ wherein each X is independently Cl or F, substitutedbutadienes of the formula CH₂ ═C(R)C(R)═CH₂ wherein each R isindependently H, C₁ to C₁₀ alkyl, Cl or F, ethylenesulfonic acidderivatives of the formula CH₂ ═CHSO₃ X wherein X is Na, K, Li, N(R)₄,H, R or (CH₂)_(n) Z where n is an integer from 1 to 10, Z is COOY, OH,N(R)₂, or SO₃ Y, Y is H, Li, Na, K or N(R) and each R is independentlyC₁ to C₁₀ alkyl, acrylamide derivatives of the formula CH₂ ═CHCON(R)₂wherein each R is independently H, C₁ to C₁₀ alkyl, or (CH₂)_(n) Z, n isan integer from 1 to 10, Z is COOY, OH, N(R₁)₂ or SO₃ Y and Y is H, Li,Na, K or N(R₁)₄ where R is C₁ to C₁₀ alkyl, methacrylamide derivativesof the formula CH₂ ═C(CH₃)CON(R)₂ wherein R is H, C₁ to C₁₀ alkyl or(CH₂) Z, n is an integer from 1 to 10, Z is COOY, OH, N(R₁)₂, SO₃ Y andY is H, Li, Na, K, or N(R₁)₄ where R.sub. 1 CH₂ ═CHOOCR, CR, wherein Ris C₁ to C₁₀ alkyl, and any and all monomer mixtures thereof.

The methacrylates and acrylates described above would thus includebranched alkyl or n-alkyl esters of C₁ -C₁₂, alcohols (for example,methyl and ethyl methacrylate and acrylate), methacrylic and acrylicacid, and allyl, glycidyl, hydroxyalkyl (for example, hydroxyethyl andhydroxypropyl), allyloxyethyl, 2,4-hexadienyl (sorbyl),dialkylaminoalkyl, fluoroalkyl, and trialkylsilylalkylene methacrylatesand acrylates.

Of the contemplated monomeric units, preferred for reasons of commericalapplicability and/or ease of synthesis are the methacrylates.

As one skilled in the art would recognize, however, each monomeric unitmust have polymerizing compatability with any adjacent monomeric units."Polymerizing compatability", as used herein, is determined by takinginto account the steric and electronic properties of particularmonomers. The polymerizing compatability of various monomers iswell-documented in the art. See, e.g., Young, L. H., "CopolymerizationReactivity Ratios" in Polymer Handbook, J. Brandrup and E. H. Immergut,eds., John Wiley & Sons, Inc. (1975). For example, α-methyl styrene doesnot have polymerizing compatablility with itself in free radicalpolymerizations above 60° C. and therefore cannot form homopolymersunder these conditions. Thus, in the macromonomer, α-methyl styrene maynot occur adjacent to another α-methyl styrene under such reactionconditions. Also, maleic anhydride, fumaronitrile, dialkyl fumarate andfumaric acid do not have any polymerizing compatability with themselvesor with each other via free radical polymerization. Thus, for example,in the macromonomer maleic anhydride may not occur adjacent to anothermaleic anhydride, fumaronitrile, dialkyl fumarate or fumaric acid.

The concentration of macromonomers in the claimed polymeric compositionis at least about 80 mol %. Contemplated thus are concentrations of atleast about 80 mol %, at Ieast aboul 85 mol %, at least about 90 mol %,at least about 95 mol %, and any and all concentrations and ranges ofconcentrations therebetween, and up to 100 mol %.

In the second embodiment, the macromonomer must have at least 50monomeric units linked to the end group when substantially all of themonomeric units in the macromonomer are selected from at least two ofthe following monomeric units:

(i) monomeric units of methacrylates;

(ii) monomeric units of methacrylonitrile; and

(iii) monomeric units of styrene.

Thus, where the macromonomer is a comacromonomer having substantiallyall of the monomeric units chosen from any combination of themethacrylates, methacrylonitrile and styrene, the macromonomer must haveat least 50 monomeric units. By "substantially", as used here, it ismeant 98% or greater. Thus, as used in the above context, the phrase"substantially all" denotes the situation where 98% or greater of all ofthe monomeric units are selected from at least two of (i) themethacrylates, (ii) methacrylonitrile or (iii) styrene.

Also in the second embodiment, the macromonomer must have at least 50monomeric units linked to the end group, when the macromonomer is ahomomacromonomer of methacrylates.

The macromonomer compositions of the present invention can be preparedby polymerization processes employing specific cobalt(II) chelates ascatalytic chain transfer agents. The cobalt(II) chelates utilized arenot only effective in controlling the molecular weights of thehomopolymers and copolymers produced, but also act to produce a polymercomposition containing a percentage of macromonomers not heretoforeknown.

The cobalt chelates utilized to produce the macromonomer compositionconsist of cobalt(II) coordinated to the following ligands: vicinaliminohydroxyimino and dihydroxyimino compounds (I), anddiazadihydroxyiminodialkyldecadienes and -undecadienes (II). By"ligand", as the term is used herein, is meant any atom, radical ormolecule which can bind to a characteristic or central element of acomplex. The structures of the aforesaid ligands are given below.##STR1## In the aforesaid formulas each R, independently, is phenyl orC₁ to C₁₂ alkyl wherein each α-carbon atom contains two hydrogen atoms,that is, is unsubstituted, and R and R on adjacent carbon atoms, takentogether, is C₅ to C₈ cycloalkylene, unsubstituted in the α-positions,--CH═CH --CH═CH--, ##STR2## R² is H or C_(x) H_(2x+1) wherein x is 1 to12; each R³, independently, is H, C_(x) H_(2x+1) wherein x is 1 to 12,or OH, with at least one being OH; and n is 2 or 3. The correspondingstructures for the cobalt chelates of these ligands are given below.More specifically, the corresponding cobalt chelate of structure I isIII, and the corresponding cobalt chelate of structure II is IV.##STR3## In formulas III and IV, R, R² and n are as defined above; eachR⁴, independently, is H or C_(x) H_(2x+1) wherein X is 1 to 12, or bothR⁴ groups taken together is --O--Z--O--; Z is BF₂, BCl₂, BBr₂ or BR₂ ² ;and X⁻ is NO₃ ⁻, Cl⁻, Br⁻, I⁻, BF₄ ⁻,PF₆ ⁻, SbF₆ ⁻ or R¹ COO⁻ wherein R¹is C₁ to C₁₂ alkyl. The cobalt chelates of the above formulas may also,but need not, be coordinated with additional ligands derived frommaterials present in the reaction medium such as water, alcohols orketones.

Preparation of iminohydroxyimino compounds, dihydroxyimino compounds,diazadihydroxyiminodialkyldecadienes anddiazadihydroxyiminodialkylundecadienes, and cobalt chelate catalyticchain transfer agents of Formulas III and IV from such iminohydroxyiminocompounds, dihydroxyimino compounds,diazadihydroxyiminodialkyldecadienes anddiazadihydroxyiminodialkylundecadienes can be accomplished using methodsknown in the art, such as those set forth in H. C. Rai et al., IndianJournal of Chemistry, Vol. 18A, 242 (1979), E. Uhlig et al., Z. anorg.allg. Chem., 343, 299 (1966), G. N. Schrauzer, Inorg. Syn., 11, 62(1968), and A. Bakac et al., J. Am. Chem. Soc., 106, 5197 (1984).

The preferred chain transfer agents herein are cobalt(II) saltscoordinated to the ligands of Formula I wherein both R⁴ groups takentogether is --O--Z--O--. Most preferred areCo(II)(2,3-dioxyiminobutane-BF₂)₂,Co(II)(1,2-dioxyiminocyclohexane-BF₂)₂, andCo(II)(1,2-diphenyl-1,2-dioxyiminoethane-BF₂)₂.

The cobalt catalyst can be employed in concentrations of between 1×10⁻⁸M and 1×10⁻³ to obtain the desired percentages of macromonomers, howeverthe optimum concentration is dependent upon the particular monomer ormonomers used and the particular concentration of macromonomer desired.For example, 1,1-substituted monomers would require less catalyst1-substituted monomers within a given system. The concentration ofmacromonomer increases with the concentration of cobalt catalystemployed.

The polymerization can be carried out either in the absence of apolymerization medium, as a bulk polymerization, or alternatively, inthe presence of a polymerization medium, as a solution, suspension oremulsion polymerization. Preferred for greater yield of macromonomer isemulsion polymerization.

Many common organic solvents are suitable as solution polymerizationmedia. These include aromatic hydrocarbons, such as benzene, toluene andthe xylenes; ethers, such as tetrahydrofuran, diethyl ether and thecommonly available ethylene glycol and polyethylene glycol monoalkyl anddialkyl ethers, including the Cellosolves and Carbitols ; alkyl estersof acetic, propionic and butyric acids; mixed ester-ethers, such asmonoalkyl ether-monoalkanoate esters of ethylene glycol; and amides suchas formamides and acid amides. In addition, ketones, such as acetone,butanone, pentanone and hexanone, are suitable, as are alcohols, such asmethanol, ethanol, propanol and butanol. Water may be used as a solventfor water soluble monomers. In some instances, it may be advantageous touse mixtures of two or more solvents.

In emulsion and suspension polymerizations, the suitable medium is waterin combination with any conventional suspending or emulsifying agent.Emulsifying agents can be anionic such as sodium dodecylsulfate orcationic such as hexadecyltrimethylammonium bromide. The suspendingagent used in the reaction can be Acrysol A-3, a polyacrylic acid madeby Rohm & Haas Company.

The bulk and solution polymerizations can be carried out at 50°-150° C.,with the preferred range 80°-110° C. The emulsion and suspensionpolymerizations can be carried out at 25°-90° C., with the preferredrange 65°-80° C.

Any of the known class of azo polymerization initiators is suitableprovided it has solubility in the solvent, monomer mixture, or water, asthe case may be, and has an appropriate half life at the temperature ofpolymerization. "Appropriate half life", as used herein, is a half lifeof about 1-4 hours. Typical of such initiators, but not restricted tothem, are azocumene, 2,2'-azobis(isobutyronitrile),2,2'-azobis(2-methyl)butanenitrile, 4,4'-azobis(4-cyanovaleric acid),and 2-(t-butylazo)-2-cyanopropane. Other soluble non-azo initiatorshaving an appropriate half life may also be used, including, amongothers, benzoyl peroxide, lauroyl peroxide, persulfates, and molecularhydrogen.

The process can be carried out as a batch or feed process. In eithertype of process the polymer is isolated by stripping off solvent andunreacted monomer or by precipitation with a nonsolvent. Alternatively,the polymer solution may be used as such if appropriate to itsapplication.

To ensure maximum catalyst activity the polymerizations should becarried out in the substantial absence of oxygen under an inertatmosphere, such as nitrogen, argon or other non-oxidizing gas."Deaeration", as the term is used herein, means the substantial removalof oxygen.

The invention is further described in the Examples set forth below. Thepolymerizations discussed therein were conducted substantially accordingto the following General Procedures, except where otherwise indicated.In the General Procedures and Examples, all parts are by moles, and alltemperatures are given in degrees Celsius, unless otherwise stated.

GENERAL POLYMERIZATION PROCEDURES A. Solution Polymerization

In a nitrogen drybox, 21.4 ml (0.2 mol) of methyl methacrylate, whichhad been previously sparged with nitrogen and passed through a column ofWoelm alumina (grade 1), was added to a 100 ml volumetric flask. To thiswas added the desired amount of cobalt catalyst and the volume wasbrought to 100 ml with distilled methanol.

To a 300 ml round bottom flask were added 0.062 g (2.5×10^("4) mol) of2,2-azobis(2-methyl)butanenitrile and the contents of the volumetricflask. The reaotion mixture was then stirred to dissolve the2,2'-azobis(2-methyl)butanenitrile and a gas chromatography (GC) samplewas taken. The round bottom flask was capped with a water cooledcondenser, brought out of the drybox and heated to reflux under nitrogenfor six hours. The reaction mixture was then allowed to cool to roomtemperature and a second GC sample was taken. The poly(methylmethacrylate) which was produced was isolated by removing solvent andmonomer from the reaction mixture via a rotary evaporator. In some ofthe examples which follow, thermal gravimetric analysis (TGA) was usedto determine the percentage of unsaturated end groups in the polymericcomposition. The procedures for TGA are set forth in Cacioli et al.,Polymer Bulletin, 11, 325-328 (1984), and the TGA data is expressed as %unsaturated end group. The accuracy of TGA is believed to be within ±3-5%, with accuracy better at the higher TGA percent unsaturation ranges.Gel permeation chromatography (GPC) was used to determine the averagemolecular weight (M_(w)) and average molecular number (M_(n)) of thepolymer produced. It should be noted that where values are less than1000, molecular weight is difficult to determine with accuracy.Nevertheless, the decrease in molecular weight shown by these values isan accurate reflection of molecular weight control. The effectiveness ofa catalytic chain transfer agent to control molecular weight correlateswith the amount of macromonomer produced. Thus, the effective molecularweight control in the presence of small catalyst amounts shown inExamples 1-27 indicates the presence of a high percentage ofmacromonomers in the resultant polymer composition.

B. Emulsion Polymerization

In a nitrogen dry box, 21.4 ml (0.2 mole) of methyl methacrylate,previously sparged with nitrogen and passed through a column of Woelmalumina (grade 1), 0.374 g 4,4'azobis(4-cyanovaleric acid) and thedesired amount of cobalt catalyst were placed into a 300 ml three neckround bottom flask equipped with a reflux condenser, septum, andmechanical stirrer. The flask was brought out of the dry box and 60 mlof 0.1M aqueous sodium dodecylsulfate (degassed) was added under anatmosphere of nitrogen. The flask was placed in a bath at 80° C., thestirrer set at 400 rpm and the reaction allowed to proceed for fourhours. A nitrogen atmosphere was maintained in the flask throughout thecourse of the reaction. After the allotted time, the reaction mixturewas cooled to room temperature and the polymer precipitated by adding150 ml of methanol. The polymer was collected by filtration, washed withmethanol, washed with water, and air dried. The data was collected asdescribed above.

EXAMPLES 1-2 A. Preparation of [CO(II)(DHIB-BF₂)₂ (H₂ O)₂ ] [DHIB=2,3dioxyiminobutane]

The title compound was prepared by the method fo A. Babac et al., J. Am.Chem. Soc., 106, 5197-5202 (1984).

The suspension resulting from the addition of 10 ml of BF₃.Et₂ O to 2 gof Co(OAc)₂.4H₂ O and 1.9 g of 2,3-dihydroxyiminobutane in 150 ml ofdiethyl ether was stirred at room temperature overnight. The resultantsolid [Co(II)(DHIB-BF₂)₂ (H₂ O₂ ] was collected by filtration, placedinto 250 ml of methanol and heated to reflux. The solid which did notdissolve was removed by filtration (0.336 g). The remaining clearsolution was placed in a freezer overnight. The crystallized product wasrecovered by filtration and dried (0.468 g). The remaining solution wasreduced to a volume of 30 ml under vacuum and placed in a freezer (-25°C.) overnight. An additional 0.101 g of product was recovered. Theinfrared spectra of the product exhibited bands at 3581 cm⁻¹ (H₂ O) and1623 cm⁻¹, 950 cm⁻¹ (BF).

B Use of [Co(II)(DHIB-BF₂ )₂ (H₂ O) as a Catalytic Chain Transfer Agentin the Free Radical Solution Polymerization of Methyl Methacrylate

The General Procedure for solution polymerization was followed using theindicated amount of Co(II)(DHIB-BF₂)₂ (H₂ O) as catalyst. The resultsare listed below.

    ______________________________________                                        Example Catalyst    -- Mn  -- Mw -- Mw/-- Mn                                                                          TGA                                   ______________________________________                                        1       5.0 × 10.sup.-6 M                                                                   2120   4790  2.26   89%                                   2       5.0 × 10.sup.-6 M                                                                   1930   3860  2.00   89%                                   ______________________________________                                    

A repeat of the above experiment with no catalyst gave Mn 45,800, Mw122,000 and Mw/Mn 2.66.

COMPARATIVE EXAMPLES A-D Attempted Use of Co(II)(DHIB-H)₂ (H₂ O)₂ asCatalytic Chain Transfer Agents in the Free Radical SoltuionPolymerization of Methyl MethacryIate

The General Procedure for solution polymerization was followed using theindicated amount of Co(II)(DHIB-H)₂ (H₂ O)₂ as catalyst. The results arelisted below.

    ______________________________________                                        Example                                                                              Catalyst   -- Mn   -- Mw  -- Mw/-- Mn                                                                          TGA                                   ______________________________________                                        A      5.0 × 10.sup.-6 M                                                                  44,300  101,000                                                                              2.27   55%                                   B      6.0 × 10.sup.-6 M                                                                  41,400  107,000                                                                              2.58   53%                                   C      6.0 × 10.sup.-6 M                                                                  29,700   65,200                                                                              2.19   60%                                   D      1.0 × 10.sup.-5 M                                                                  19,000   48,600                                                                              2.56   72%                                   ______________________________________                                    

A repeat of the above experiment with no catalyst gave Mn 45,800, Mw122,000 and Mw/Mn 2.66 and TGA 52%.

EXAMPLE 3 The Use of Co(II)(DHIB-BF₂ (H₂ O)₂ as a Catalytic ChainTransfer Agent in the Free Radical Solution Polymerization of MethylMethacrylate

The General Procedure for solution polymerization was followed using theindicated amount of Co(II)(DHIB-BF₂)₂ (H₂ O)₂ as catalyst, methylmethacrylate as monomer, 2,2'-azobis(isobutyronitrile) as initiator, andmethyl ethyl ketone as solvent. The cobalt catalyst was preparedaccording to the procedure described in Examples 1-2. The results arelisted below.

    ______________________________________                                        Example Catalyst    -- Mn  -- Mw -- Mw/-- Mn                                                                          TGA                                   ______________________________________                                        3       5 × 10.sup.-6 M                                                                     1,020  2,110 2.07   99%                                   ______________________________________                                    

EXAMPLE 4 The Use of Co(II)(DHIB-BF₂ (₂ (H₂ O)₂ as a Catalytic ChainTransfer Agent in the Free Radical Solution Polymerization of MethylMethaorylate

In a nitrogen drybox, 1000 ml of methyl methacrylate, which had beenpreviously sparged with nitrogen and passed through a column of Woelmalumina (grade 1) was added to a 2000 ml round bottom flask. To this wasadded 4.2 mg of Co(II)(DHIB-BF₂)₂ (H₂ O)₂ catalyst, 2.90 g of2,2-azobis(2-methyl)butanenitrile and 475 ml of methyl ethyl ketone. Theround bottom flask was capped with a water cooled condenser, brought outof the drybox and heated to 65° C. under ntirogen for 17.5 hours. Thereaction mixture was then allowed to cool to room temperature. Themethyl methacrylate homomacromonomer produced was isolated with theGeneral Procedure for solution polymerization was then conducted. Theresults are as follows.

    ______________________________________                                        Example Catalyst  -- Mn   -- Mw -- Mw/-- Mn                                                                           TGA                                   ______________________________________                                        4       1.0 ppm   5,230   8,040 1.63    95%                                   ______________________________________                                    

COMPARATIVE EXAMPLES E-F

Attempted Use of Co(II)(DHIB-H)₂ (Ph₃ P) and Co(II)(DHIB-H)₂ (C₅ H₅ N)as Catalystic Chain Transfer Agents in the Free Radical SolutionPolymerization of Methyl Methacrylate

[Ph₃ P=Triphenyl phosphine]

The General Procedure for solution polymerization was followed using theindicated type and amount of Co(II) catalyst. The results are listedbelow.

    ______________________________________                                        Example Catalyst      -- Mn    -- Mw -- Mw/-- Mn                              ______________________________________                                        E       Co(II)(DHIB-H).sub.2                                                                        24,600   56,800                                                                              2.31                                             (Ph.sub.3 P)                                                          F       Co(II)(DHIB-H).sub.2                                                                        39,500   82,100                                                                              2.08                                             (C.sub.5 H.sub.5 N)                                                   ______________________________________                                    

EXAMPLES 5-7 The Use of Co(II)(DHIB-BF₂)₂ (H₂ O)₂ as a Catalystic ChainTransfer Agent in the Free Radical Solution Polymerization of MethylAcrylate

The General Procedure for solution polymerization was followed using theindicated amount of Co(II)(DHIB-BF₂)₂ (H₂ O)₂ as catalyst, methylacrylate as monomer, 2,2'-azobis(isobutyronitrile) as initiator andmethyl ethyl ketone as solvent. The cobalt catalyst was preparedaccording to the procedure described in Examples 1-2. The results arelisted below.

    ______________________________________                                        Example   Catalyst  -- Mn     -- Mw -- Mw/-- Mn                               ______________________________________                                        5         5 × 10.sup.-6 M                                                                   14,600    48,600                                                                              3.33                                      6         5 × 10.sup.-5 M                                                                   7,700     23,300                                                                              3.03                                      7         5 × 10.sup.-4 M                                                                   1,620      4,380                                                                              2.70                                      ______________________________________                                    

A repeat of the above experiment with no catalyst gave Mn 17,300, Mw56,500 and Mw/Mn 3.27.

EXAMPLES 8-10 The Use of Co(II)(DHIB-BF₂)₂ (H₂ O)₂ as a Catalytic ChainTransfer Agent in the Free Radical Solution Polymerization of EthylAcrylate

The General Procedure for solution polymerization was followed using theindicated amount of Co(II)(DHIB-BF₂)₂ (H₂ O)₂ as catalyst, ethylacrylate as monomer, 2,2'-azobis(isobutyronitrile) as initiator, andmethyl ethyl ketone as solvent. The cobalt catalyst was preparedaccording to the procedure described in Examples 1-2. In the resultslisted below, [η] measured in dl/g is the intrinsic viscosity which isproportional to molecular weight. The higher the value of [η], thehigher the molecular weight. These values were determined by capillaryviscometry (CV).

    ______________________________________                                        Example                                                                              Catalyst   -- Mn   -- Mw  -- Mw/-- Mn                                                                          [η]                               ______________________________________                                        8      5 × 10.sup.-6 M                                                                    15,500  61,500 3.97   0.2151                                9      5 × 10.sup.-5 M                                                                    9,760   33,700 3.45   0.1509                                10     5 × 10.sup.-4 M                                                                    1,910    5,510 2.88   0.0556                                ______________________________________                                    

A repeat of the above experiment with no catalyst gave Mn 20,200, Mw70,500, Mw/Mn 3.49, and [η] 0.2388

EXAMPLES 11-13 The Use of Co(II)(DHIB-BF₂)₂ (H₂ O)₂ as a Catalytic ChainTransfer Agent in the Free Radical Solution Polymerization of t-ButylAcrylate

Examples 8-10 were repeated using t-butyl acrylate as monomer. Theresults are listed below.

    ______________________________________                                        Example                                                                              Catalyst   -- Mn   -- Mw  -- Mw/-- Mn                                                                          [η]                               ______________________________________                                        11     5 × 10.sup.-6 M                                                                    15,000  71,100 4.75   0.2088                                12     5 × 10.sup.-5 M                                                                    14,100  58,600 4.16   0.1840                                13     5 × 10.sup.-4 M                                                                     4,400  12,300 2.81   0.0761                                ______________________________________                                    

A repeat of the above experiment with no catalyst gave Mn 16,000, Mw74,200, Mw/Mn 4.64, and [η] 0.2122.

EXAMPLES 14-16 The Use of Co(II)(DHIB-BF₂)₂ (H₂ O)₂ as a Catalytic ChainTransfer Agent in the Free Radical Solution Polymerization of VinylAcetate

The General Procedure for solution polymerization was followed using theindicated amount of Co(II)(DHIB-BF₂)₂ (H₂)₂ as catalyst, vinyl acetateas monomer, 2,2'-azobis(isobutyronitrile) as initiator and methyl ethylketone as solvent. The cobalt catalyst was prepared according to theprocedure described in Examples 1-2. The results are listed below.

    ______________________________________                                        Example    Catalyst  -- Mn    -- Mw                                                                              -- Mw/-- Mn                                ______________________________________                                        14         5 × 10.sup.-6 M                                                                   1,610    3,420                                                                              2.12                                       15         5 × 10.sup.-5 M                                                                   1,660    3,510                                                                              2.11                                       16         5 × 10.sup.-4 M                                                                     891    2,120                                                                              2.38                                       ______________________________________                                    

A repeat of the above experiment with no catalyst gave Mn 1,660, Mw3,579 and Mw/Mn 2.16.

EXAMPLES 17-19 The Use of Co(II)(DHIB-BF₂)₂ (H₂ O)₂ as a Catalytic ChainTransfer Agent in the Free Radical Solution Polymerization ofAcrylonitrile

The General Procedure for solution polymerization was followed using theindicated amount of Co(II)(DHIB-BF₂)₂ (H₂ O)₂ as catalyst, acrylonitrileas monomer, 2,2'-azobis(isobutyronitrile) as initiator and methyl ethylketone as solvent. The cobalt catalyst was prepared according to theprocedure described in Examples 1-2. [η] is defined in Examples 8-10.

    ______________________________________                                        Example        Catalyst  [η]                                              ______________________________________                                        17             5 × 10.sup.-6 M                                                                   0.5465                                               18             5 × 10.sup.-5 M                                                                   0.5410                                               19             5 × 10.sup.-4 M                                                                   0.4483                                               ______________________________________                                    

A repeat of the above experiment with no catalyst gave [η] 0.5533.

EXAMPLE 20 The Use of Co(II)(DHIB-BF₂)₂ (H₂ O)₂ as a Catalytic ChainTransfer Agent in the Free Radical Solution Polymerization of2-Acrylamido-2-methylpropanesulfonic Acid

The General Procedure for solution polymerization was followed using theindicated amount of Co(II)(DHIB-BF₂)₂ (H₂ O)₂ as catalyst, 0.1 mole2-acrylamido-2-methylpropanesulfonic acid as monomer, 1.0×10⁻³ moles of2,2'-azobis(isobutyronitrile) as initiator and 100 ml ofdimethylformamide as solvent. The cobalt catalyst was prepared accordingto the procedure described in Examples 1-2. The contents were heated at100° C. under a nitrogen atmosphere for 90 minutes. The result, listedbelow, was determined by CV. [η] is defined in Examples 8-10.

    ______________________________________                                               Catalyst                                                                              [η]                                                        ______________________________________                                               5 × 10.sup.-4 M                                                                 0.1150                                                         ______________________________________                                    

A repeat of the above experiment with no catalyst gave [η] 0.1525.

EXAMPLE 21 The Use of Co(II)(DHIB-BF₂)₂ (H₂ O) as a Catalytic ChainTransfer Agent in the Free Radical Solution Polymerization of2-Acrylamido-2-methylpropanesulfonic Acid

The General Procedure for solution polymerization was followed using theindicated amount of Co(II)(DHIB-BF₂)₂ (H₂ O)₂ as catalyst, 0.1 mole of2-acrylamido-2-methylpropanesulfonic acid as monomer, 0.374 g of4,4'-azobis(4-cyanovaleric acid) as the initiator and 100 ml of water assolvent. The cobalt catalyst was prepared according to the proceduredescribed in Examples 1-2. The contents were heated at 100° C. under anitrogen atmosphere for 30 minutes. The result, listed below, wasdetermined by CV. [η] is in Examples 8-10.

    ______________________________________                                               Catalyst                                                                              [η]                                                        ______________________________________                                               5 × 10.sup.-4 M                                                                 0.5832                                                         ______________________________________                                    

A repeat of the above experiment with no catalyst gave [η] dl/g 0.8078.

EXAMPLES 22-23 The Use of Co(II)(DHIB0BF₂)₂ (H₂ O)₂ as a Catalytic ChainTransfer Agent in the Free Radical Emulsion Polymerization of MethylMethacrylate

The General Procedure for emulsion polymerization was followed using theindicated amount of Co(II)(DHIB-BF₂)₂ (H₂ O)₂ as catalyst andhexadecyltrimethylammonium bromide [0.025 M] as the cationic emulsifier.The cobalt catalyst was prepared according to the procedure described inExamples 1-2. The results are listed below.

    ______________________________________                                        Example  Catalyst  -- Mn     -- Mw -- Mw/-- Mn                                ______________________________________                                        22       0.25   ppm    154,000 647,000                                                                             4.20                                     23       2.5    ppm     20,000  44,900                                                                             2.25                                     ______________________________________                                    

A repeat of the above experiment with no catalyst gave Mn 368,000, Mw3,655,000 and Mw/Mn 9.93.

EXAMPLE 24 A. Preparation of Co(II)(DDE-H)₂ (H₂ O)₂[DDE=1,2-diphenyl-1,2-dioxyiminoethane]

Co(II)(DDE-H)₂ (H₂ O)₂ was prepared by the method of G. N. Schrauzer,Inorg. Syn., 11, 64 (1968).

B. Preparation of CO(II)DDE-BF₂)₂ (H₂ O)₂

In a dry box, Co(II)(DDE-H)₂)₂ (H₂ O)₂ [5.0 g], BF₃.O(C₂ H₅)₂ [10.0 ml]and 100 ml (C₂ H₅)₂ O were placed into a round bottom flask. Thecontents were stirred for 24 hours after which time the suspended solidswere recovered by filtration and washed with diethyl ether. Therecovered solids were dried under vacuum. Product yield=5.56 g.

C. The Use of Co(II)(DDE-BF₂)₂ (H₂ O)₂ as a Catalytic Chain TransferAgent in the Free Radical Emulsion Polymerization of Methyl Methacrylate

The General Procedure for emulsion polymerization was followed. Theconcentration of Co(II)(DDE-BF₂)₂ (H₂ O)₂ was 2.5 ppm. The resultingpolymer had Mn 171,000, Mw 1,349,000 and Mw/Mn 7.88.

EXAMPLE 25 A. Preparation ofCo(II)(DC-H)₂ (H₂ O)₂[DC=,2-dioxyiminocyclohexane]

Co(II)(DC-H)₂ (H₂ O)₂ was prepared by the method of G. N. Schrauzer,Inorg. Syn., 11, 64 (1968).

B. Preparation of Co(II)(DC-BF₂)₂ (H₂ O)₂

In a dry box, Co(II)(DC-H)₂ (H₂ O)₂ [5.0 g], BF₃.O(C₂ H₅)₂ [10.0 ml])and 100 ml of (C₂ H₅)₂ O were placed into a round bottom flask. Thecontents were stirred for 24 hours after which time the suspended solidswere recovered by filtration and washed with diethyl ether. Therecovered solids were dried under vacuum. Product yield=4.09 g.

C. The Use of Co(II)(DC-BF₂)₂ (H₂ O)₂ as a Catalystic Chain TransferAgent in the Free Radical Emulsion Polymerization of Methyl Methacrylate

The General Procedure for emulsion polymerization was followed. Theconcentration of Co(II)(DC-BF₂)₂ (H₂ O)₂ was 2.5 ppm. The resultingpolymer had Mn 14,500, Mw 31,500 and Mw/Mn 2.17.

EXAMPLES 26-27 The Use of Co(II)(DHIB-BF₂)₂ (H₂ O)₂ as a Catalytic ChainTransfer Agent in the Free Radical Emulsion Polymerization of MethylMethacrylate

The General Procedure for emulsion polymerization was followed using theindicated amount of Co(II)(DHIB-BF₂)₂ (H₂ O)₂ as catalyst and 0.037 g ofinitiator. The cobalt catalyst was prepared according to the proceduredescribed in Examples 1-3. The results are listed below.

    ______________________________________                                        Example Catalyst  -- Mn   -- Mw  -- Mw/-- Mn                                                                          TGA                                   ______________________________________                                        26      2.5   ppm     25,700                                                                              54,500 2.12   100%                                27      25    ppm     1,260 3,280  2.61   100%                                ______________________________________                                    

A repeat of the above experiment with no catalyst gave Mn 2,926,000, Mw7,002,000 and Mw/Mn 2.39.

COMPARATIVE EXAMPLES G-I Attempted Use of Co(II)(DHIB-H)₂ (H₂ O)₂,KCo(CN)₅ and Co(II)Salen as Catalytic Chain Transfer Agents in the FreeRadical Emulsion Polymerization of Methyl Methacrylate[Salen=N,N'-bis(salicylidene)ethylenediamines]

The General Procedure for emulsion polymerization was followed using theindicated type and amount of Co(II) catalyst andhexadecyltrimethylammonium bromide [0.025 M] as the cationic emulsifier.The results are listed below.

    ______________________________________                                        Example Catalyst      -- Mn   -- Mw  -- Mw/-- Mn                              ______________________________________                                        G       Co(II)(DHIB- 281,000  3,799,000                                                                            13.5                                             H).sub.2 (H.sub.2 O)                                                          [50 ppm]                                                              H       Co(II)Salen  372,000  3,794,000                                                                            10.2                                             [500 ppm]                                                             I       K.sub.3 Co(CN).sub.5                                                                       256,000  3,607,000                                                                            14.1                                             [50 ppm]                                                              ______________________________________                                    

A repeat of the above experiment with no catalyst gave Mn 368,000, Mw3,655,000, and M w/Mn 9.93.

INDUSTRIAL APPLICABILITY

The macromonomers of the present invention can be employed to producegraft polymers which are useful in coating and molding resins. Otherpotential uses can include cast, blown, spun or sprayed applications infiber, film, sheet, composite materials, multilayer coatings,photopolymerizable materials, photoresists, surface active agentsincluding soil repellants an physiologically active surfaces, adhesives,adhesion promoters and coupling agents, among others. End productstaking advantage of available characteristics can include lacquers,enamels, electrocoat finishes, high solids finishes, aqueous or solventbased finishes, clear or filled acrylic sheet or castings, includingautomotive and architectural glazing and illumination housings andrefractors, additives for oil and fuel, including antimisting agents,outdoor and indoor graphics including signs and billboards and trafficcontrol devices, reprographic products and many others.

Using standard polymerization techniques, these graft polymers can besynthesized by reacting one or more macromonomers of the invention withone or more monomers having polymerizing compatibility with themacromonomers and with each other.

I claim:
 1. A composition comprising: at least about 85 mol % of amacromonomer having(I) an end group of the formula CH₂ ═C(X₃)(CH₂), and(II) at least 50 and up to about 10,000 monomeric units linked to theend group, said units being independently selected from a compound ofthe fomula --CH₂ C(R₄)(R₅)); wherein X₃ is CO₂ J; wherein each R₄ and R₅are CO₂ J and CH₃, provided that when R₄ is CO₂ J, R₅ is CH₃ and when R₅is CO₂ J, R₄ is CH₃ ; and wherein each J is independently C₁ to C₁₂alkyl, allyl, glycidyl, hydroxyalkyl, allyloxyethyl, 2,4-hexadienyl ordialkylaminoalkyl; provided that each monomeric unit has polymerizingcompatibility with any adjacent monomeric unit.
 2. The composition ofclaim 1 wherein the number of monomeric units is at least 50 and up toabout 1,000.
 3. The composition of claim 2 wherein the number ofmonomeric units is at least 100 and up to about
 500. 4. The compositionof claim 1 wherein J is CH₃.
 5. The composition of claim 1 wherein themacromonomer comprises at least about 90 mol %.
 6. The composition ofclaim 5 wherein the macromonomer comprises at least about 95 mol %. 7.The composition of claim 4 wherien the macromonomer comprises at leastabout 90 mol %.
 8. The composition of claim 7 wherein the macromonomercomprises at least about 95 mol %.